CN105051947A - High voltage lithium ion battery - Google Patents

High voltage lithium ion battery Download PDF

Info

Publication number
CN105051947A
CN105051947A CN201480016049.4A CN201480016049A CN105051947A CN 105051947 A CN105051947 A CN 105051947A CN 201480016049 A CN201480016049 A CN 201480016049A CN 105051947 A CN105051947 A CN 105051947A
Authority
CN
China
Prior art keywords
composite material
group
component
members
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201480016049.4A
Other languages
Chinese (zh)
Inventor
J.J.刘
M.G.雷罗夫斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of CN105051947A publication Critical patent/CN105051947A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A lithium ion battery cathode material, and an electrode prepared from such material, is described. The lithium ion battery operates at a high voltage up to about (i.e. up to 5 V) and has a desirably high cycling performance and rate capability. The invention relates to the field of lithium ion batteries. More specifically, the invention relates to a lithium ion battery comprising lithium-based composite cathodes.

Description

High-voltage lithium ion storage battery
Technical field
The present invention relates to lithium-ions battery field.More specifically, the present invention relates to the lithium-ions battery of the composite cathode comprised based on lithium.
Background technology
Along with the progress of portable electric appts and the strong interest to plug-in blended electric power automobile, there is the very big demand for increasing lithium-ions battery energy and power capacity.In this regard, 5V spinel cathode LiMn 2-xm xo 4(wherein M is such as Co, Cr, Ni, Fe, Cu or Ga, and x is about 0.5) has caused very large concern, and this spreads by by 3 dimension lithium ions in spinel crystal lattice its high operation voltage and the intrinsic multiplying power property of height of providing.In addition, because it comprises less Mn in the material 3+, so at LiMn 2-xm xo 4in inhibit due to manganese dissolve and 4VLiMn 2o 4jahn-Teller distortion in negative electrode and the difficulty that runs into.In this regard, 5V spinel cathode such as LiMn 1.5ni 0.5o 4cause very big concern, this is due to the almost smooth operating voltage close to 5V with by Ni 2+/3+and Ni 3+/4+the high power capacity of the acceptance made us that the operation of redox couple produces.
But, even LiMn 2-xm xo 4active material of cathode also suffers stability problem, at the LiMn of cation ordering when including 1.5ni 0.5o 4the structural instability sex chromosome mosaicism found in material, and sometimes because electrolyte reacts the surface instability problem caused.Such as these problem significantly can reduce chemical property.
Propose to replace LiMn by other element such as Li, Al, Mg, Ti, Cr, Fe, Co, Cu, Zn or Mo part 1.5ni 0.5o 4in Mn and/or Ni improve cyclicity.Some in these situations improve cyclicity, and this is the stability due to spinel crystal lattice in the cationic disordering situation in 16d octahedral sites, and the less lattice parameter difference between three cubics phases of cycle period formation.Although LiMn 1.5ni 0.5o 4structural stability replace by suitable cationic moiety and improve, but surface instability still retains as problem.
Therefore, still need as by LiMn 1.5m 0.5o 4the performance reaching the improvement of balance between multifrequency nature that spinel cathode material shows.
Summary of the invention
Theme of the present disclosure meets above-mentioned needs by providing various favourable technique effect, and wherein said technique effect comprises:
There is provided electrode material, such as active material of cathode, it shows advantageously high charge/electric discharge and cycle performance and well balanced advantageously between high-rate characteristics, and
There is provided electrode material, such as based on LiMn 1.5m 0.5o 4the active material of cathode of spinel, wherein stability problem wherein solves to form composite cathode material by being mixed with other lithium-containing materials by spinel.
Therefore, an embodiment of theme of the present disclosure provides by the composite material of the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5,
W is 0 to about 0.6;
M comprises one or more members of the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1.
In a specific embodiment of above-mentioned composite material, composite material can by with the representation of following formula IV:
x(Li 2-wA 1-vB w+vO 3-e)·(1-x)(Li yMn 2-zM zO 4-d)IV
Wherein A, B, e, v, w, M, d, y and z are as implied above, and x is about 0.005 to about 0.08.
In another embodiment of its theme, provide a kind of electrode for electrochemical cell, it comprises the composite material by the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises one or more members of the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5,
W is 0 to about 0.6;
M comprises one or more members of the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1; And
Wherein when existing as the negative electrode had in the electrochemical cell of lithium anodes, be charged to relative to Li/Li +the de-lithiumation of electrode experience of 4.8V voltage, thus make to be expressed as (Li 2-wa 1- vb w+vo 3-e) the component of composite material be represented as (Li 2-w-ga 1-vb w+vo 3-e-g/2), wherein g is less than about 0.2.
In another embodiment of theme of the present disclosure, provide a kind of electrode for electrochemical cell, it comprises the composite material by the representation of Formula Il I:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises one or more members of the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5,
W is 0 to about 0.6;
M comprises one or more members of the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1; And
Wherein when existing as the negative electrode had in the electrochemical cell of lithium anodes, described electrode
A () is being enough to from being expressed as (Li ymn 2-zm zo 4-d) composite material component in remove Li +under the voltage of ion, be charged to y and be reduced to the degree being less than 0.2, and
B () is then discharged to relative to Li/Li with the multiplying power of the composite material of 10mA/g +the voltage of reference electrode 3.5V,
Participate in the electric discharge of electrochemical cell, make to be attributable to be expressed as (Li 2-wa 1-vb w+vo 3-e) nanocomposite constituents about 90mAh/g is less than to the contribution of discharge capacity.
In another embodiment of theme of the present disclosure, provide by the composite material of the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5,
W is 0 to about 0.6;
M comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1;
Wherein said composite material is characterized by XRD as follows:
In another embodiment of its theme, in any one composite material represented by formula III or IV described herein, (Li 2-wa 1vb w+vo 3-e) component can have layer structure, and/or (Li ymn 2-zm zo 4-d) component can have spinel structure.
In another embodiment of its theme, provide electrochemical cell, such as lithium ion battery, described lithium-ions battery comprises: (a) shell; (b) anode and negative electrode, described anode arranges in the housing with negative electrode and ionic conduction contacts each other, and wherein said negative electrode comprises composite material as described herein; C () arranges in the housing and provides the non-aqueous electrolyte composition of the ionic conduction path between described anode and described negative electrode; (d) porous barrier between described anode and described negative electrode.
Accompanying drawing explanation
Fig. 1 is 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4the X-ray diffraction figure of composite material.
Fig. 2 is by the 0.03Li of test as cathode material 2mnO 30.97LiMn 1.5ni 0.5o 4the charge-discharge curves that composite material obtains.
Fig. 3 is LiMn 1.5ni 0.5o 4the X-ray diffraction figure of compound.
Fig. 4 is by the LiMn of test as cathode material 1.5ni 0.5o 4the charge-discharge curves that compound obtains.
Fig. 5 is 0.1Li 2mnO 30.9LiMn 1.5ni 0.5o 4x-ray diffraction (XRD) figure of composite material.
Fig. 6 is by the 0.1Li of test as cathode material 2mnO 30.9LiMn 1.5ni 0.5o 4the charge-discharge curves that composite material obtains.
Fig. 7 is 0.5Li 2mnO 30.5LiMn 1.5ni 0.5o 4the X-ray diffraction figure of composite material.
Fig. 8 is by the 0.5Li of test as cathode material 2mnO 30.5LiMn 1.5ni 0.5o 4the charge-discharge curves that composite material obtains.
Fig. 9 compares LiMn 1.5ni 0.5o 4compound, 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4composite material, 0.1Li 2mnO 30.9LiMn 1.5ni 0.5o 4composite material and 0.5Li 2mnO 30.5LiMn 1.5ni 0.5o 4the cycle performance of composite material.
Figure 10 compares LiMn 1.5ni 0.5o 4compound, 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4composite material, 0.1Li 2mnO 30.9LiMn 1.5ni 0.5o 4composite material and 0.5Li 2mnO 30.5LiMn 1.5ni 0.5o 4the multiplying power property of composite material.
Figure 11 is 0.03Li 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the X-ray diffraction figure of composite material.
Figure 12 is 0.03Li 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the scanning electron micrograph of composite material.
Figure 13 is by the 0.03Li of test as cathode material 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the charge-discharge curves that composite material obtains.
Figure 14 illustrates when testing as cathode material, 0.03Li 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the cycle performance of composite material.
Figure 15 a illustrates when testing under various discharge current density as cathode material, 0.03Li 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the multiplying power property of composite material.
Figure 15 b is when testing as cathode material, 0.03Li 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the figure of the discharge capacity of composite material under different C multiplying power.
Embodiment
Except as otherwise noted, as used in whole specification that is above and theme herein, following term will be defined as follows:
" anode " refers to the electrochemical cell electrode that oxidation wherein occurs when discharging.At primary cell, in such as storage battery, anode is electronegative electrode.
" negative electrode " refers to the electrochemical cell electrode that reduction wherein occurs when discharging.At primary cell, in such as storage battery, negative electrode is the electrode of positively charged.
" electrolytic salt " refers to ion salt, and it dissolves in the solvent of non-aqueous electrolyte composition at least in part and be dissociated into ion at least in part in the solvent of non-aqueous electrolyte composition, to form conductivity electrolyte composition.
" lithium-ions battery " refers to rechargeable electrochemical cell type, and wherein lithium ion moves from negative electrode anode between charge period, and at interdischarge interval from anode to movable cathode.Storage battery can for being arranged to the set of the one or more batteries providing electric energy.The battery of storage battery can be arranged by various structure (such as, series, parallel and combination thereof).
" non-aqueous electrolyte " composition refers to the electrolytical Chemical composition that be suitable as in lithium-ions battery.Described electrolyte composition comprises at least one non-aqueous solvent and at least one electrolytic salt usually.
Disclosed herein is the composite material of the mixture comprising different lithium compound.Composite material can be formed as such as composition of matter, and one (component I) in the component of the mixture be made up of this class composite material can by with the representation of following formula I:
(Li 2-wA 1-vB w+vO 3-e)
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5; And
W is 0 to about 0.6.
Another kind (component I I) in the component of the mixture be made up of this class composite material can by with the representation of Formula Il:
(Li yMn 2-zM zO 4-d)II
Wherein:
M comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1.
Therefore, in an embodiment of its theme, provide a kind of composite material, it is by preparing said components combination or mixing, and wherein said composite material can by the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5,
W is 0 to about 0.6;
M comprises one or two member in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1.
In other embodiments various of its theme, provide a kind of multiple material, it is by preparing said components (component I and II) combination or mixing with relative quantity, makes described composite material can by with the representation of following formula IV:
x(Li 2-wA 1-vB w+vO 3-e)·(1-x)(Li yMn 2-zM zO 4-d)IV
Wherein x is about 0.005 to about 0.08; And A, B, e, v, w, M, d, y and z are as implied above.In another embodiment, x can be about 0.005 or higher, can be maybe about 0.01 or higher, can be maybe about 0.015 or higher, can be maybe about 0.02 or higher, can be maybe about 0.03 or higher, and can also be about 0.08 or lower, can be maybe about 0.07 or lower, can be maybe about 0.06 or lower, can be maybe about 0.05 or lower.In another embodiment, x can in the scope of about 0.005 to about 0.08, or in the scope of about 0.01 to about 0.07, or in the scope of about 0.015 to about 0.06, or in the scope of about 0.02 to about 0.05.
In the various preferred embodiments of its theme, advantageously high charge/electric discharge and cycle performance is shown for providing, and the object of the advantageously well balanced composite material of high-rate characteristics, expect to prepare a kind of composite material, wherein component I and II involved with relative quantity described above.
In another embodiment of its theme, provide by the composite material of the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein A, B, e, v, w, M, d, y and z are as implied above, and
Wherein said composite material is characterized by following X-ray diffractogram: // // // // // ///
In another embodiment of its theme, in any one composite material represented by formula III or IV described herein, or in its component of any one described in formula I and II, (Li 2-wa 1vb w+vo 3-e) component can have layer structure, and/or (Li vm n2-zm zo 4-d) component can have spinel structure.
Work as Li 2-wb w+va 1-vo 3-ewhen component has layer structure, some in lithium ion occupy 16c octahedral sites, and remaining lithium ion occupies 16d octahedron (transition-metal cation) case.A and B cation also occupies 16d octahedral sites.But, Li and A in some the replaceable structures in B cation.Cation at 16d octahedral sites place and the cation being mainly lithium at 16c octahedral sites place occupy plane alternately, and give material layer structure.The two-dimensional framework that layered structure provides lithium ion to spread.In various specific embodiment, A and B all occupies octahedral sites.As by Li 2-wb w+va 1-vo 3-ea typical case of the stratified material that component provides is Li 2mnO 3.
Work as Li ymn 2-zm zo 4-dwhen component has spinel structure, when 0 < y <=1, lithium ion can occupy 8a tetrahedral sites, and when 1 < y <=2, can occupy 16c octahedral sites.Mn and M cation occupies the 16d octahedral sites of the closelypacked oxygen array of cubic.The three-dimensional framework that the interconnected void case of the closelypacked oxygen array of cubic provides lithium ion to spread.As by Li vmn 2- zm zo 4-da typical case of the spinel that component provides is LiMn 1.5ni 0.5o 4.
In other embodiments, the Li of its composite material ymn 2-zm zo 4-dcomponent can be cation disorder, or has cation disorder structure.In " cation disorder " structure, Mn and M is positioned at the 16d case of Fd3 (bar) m structure at random.Cation disorder structure has low lattice strain during lithium inserts and extracts.
Because the space being applicable to the various components of its (as mentioned above) composite material is arranged, also provide by with the composite material of the representation of Formula Il in other embodiments:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein A, B, e, v, w, M, d, y and z are as implied above, and
Wherein component I (Li 2-wa 1vb w+vo 3-e) component has layer structure, and component I I (Li vmn 2- zm zo 4-d) component has spinel structure.In addition, have layer structure and component I I has in above-described embodiment of spinel structure in component I, the content of the component of composite material can by with the representation of following formula IV:
x(Li 2-wA 1-vB w+vO 3-e)·(1-x)(Li yMn 2-zM zO 4-d)IV
Wherein x, A, B, e, v, w, M, d, y and z are as implied above.
In the various specific embodiments of its theme, in any one composite material represented by formula III or IV described herein, or in its component of any one described in formula I and II,
A is Mn, A for Ti or A is Mn and Ti; And/or
B is the one or more members in the group be made up of Al, Co, Cr, Cu, Fe, Ga, Mg, Ni, Ti, V and Zn; And/or
B is the one or more members in the group be made up of Co, Cr, Cu, Fe, Ga, Ni and V; And/or
B is the one or more members in the group be made up of Co, Cu, Fe, Ga and Ni; And/or
B is one or two member in the group be made up of Fe and Ni; And/or
E is 0; Or e is greater than 0; Or e is 0 or higher, or be about 0.01 or higher, or be about 0.05 or higher, or be about 0.1 or higher, and be also about 0.3 or lower, or be about 0.25 or lower, or be about 0.2 or lower; And/or
V is 0; Or V is greater than 0; Or V is 0 or higher, or be about 0.01 or higher, or be about 0.05 or higher, or be about 0.1 or higher, or be about 0.2 or higher, and be also about 0.5 or lower, or be about 0.4 or lower, or be about 0.3 or lower, or be about 0.2 or lower; And/or
W is 0; Or w is greater than 0; Or w is 0 or higher, or be about 0.01 or higher, or be about 0.05 or higher, or be about 0.1 or higher, or be about 0.2 or higher, and be also about 0.6 or lower, or be about 0.5 or lower, or be about 0.4 or lower; And/or
M is the one or more members in the group be made up of Al, Co, Cr, Cu, Fe, Ga, Mg, Ni, Ti, V and Zn; And/or
M is the one or more members in the group be made up of Co, Cr, Cu, Fe, Ga, Ni and V; And/or
M is the one or more members in the group be made up of Co, Fe, Ga and Ni; And/or
M is the one or more members in the group be made up of Fe and Ni; And/or
D is 0; Or d is greater than 0; Or d is 0 or higher, or be about 0.01 or higher, or be about 0.05 or higher, or be about 0.1 or higher, or be about 0.2 or higher, and be also about 0.5 or lower, or be about 0.4 or lower, or be about 0.3 or lower, or be about 0.2 or lower; And/or
Y is 0; Or y is greater than 0; Or y is 0 or higher, or be about 0.01 or higher, or be about 0.05 or higher, or be about 0.1 or higher, or be about 0.3 or higher, and be also about 1 or lower, or be about 0.9 or lower, or be about 0.8 or lower; And/or
Z is about 0.3 or higher, or is about 0.4 or higher, or is about 0.5 or higher, and is also about 1 or lower, or is about 0.9 or lower, or is about 0.8 or lower.
Various conventional method can be used to prepare composite material as disclosed herein.Liu and Manthiram, Chem.Mater.2009,21,1695 ~ 1707 disclose coprecipitation method, it relates to by adding KOH, afterwards with the heat/cool rates of 1 DEG C/min at 900 DEG C in atmosphere by through the hydroxide precursor of oven drying and LiOHH20 roasting 12 hours, carry out the hydroxide precursor of the acetate of the component metals (such as manganese, nickel, iron, gallium, cobalt and/or copper) of precipitate composite material.US5,738,957 (Amine) disclose solid-state approach, and it relates at about 450 DEG C, at the temperature of preferably 600 DEG C ~ 1000 DEG C in atmospheric environment or air or oxygen the mixture of the oxide of the component metals of roasting composite material, hydroxide, carbonate and nitrate precursors; And disclosing sol-gel process, it relates to the acetate of the component metals of composite material, nitrate, sulfate, acylate (such as formates, oxalates or citrate) and/or the mixture of inorganic acid salt in ethanol or water.Carbon black can be used as gel stabilizer.Add ammoniacal liquor, and will precipitate dry in Rotary Evaporators under vacuo, and then can roasting at 400 DEG C in atmosphere as required.In its composite material, by their preparation method, two kinds of components are structurally integrated and/or physical mixed and blended to form composite material.
Composite material disclosed herein is suitable as the electroactive material in electrochemical cell, such as active material of positive electrode or active material of cathode.Therefore, there is disclosed herein the electrode for electrochemical cell, wherein said electrode is prepared by its composite material.In a preferred embodiment, its composite material is for the preparation of the negative electrode in electrochemical cell.
Therefore, in an embodiment of the electrode for electrochemical cell, provide electrode (such as negative electrode) herein, it comprises the composite material by the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein A, B, e, v, w, M, d, y and z are as implied above.Comprise in other embodiment of electrode in an electrochemical cell what obtained by composite material as above, composite material also can by with the representation of following formula IV:
x(Li 2-wA 1-vB w+vO 3-e)·(1-x)(Li yMn 2-zM zO 4-d)IV
Wherein x, A, B, e, v, w, M, d, y and z are as implied above.
The electrode be made up of composite material as described herein can in lithium battery electrochemical activation.It is believed that the electrochemical reaction part of charging to battery passes through to extract lithium ion adjoint by Ni 2+be oxidized to Ni 4+, manganese ion keeps tetravalence to carry out simultaneously, but part is also undertaken by the oxygen in extraction lithium simultaneously loss structure.The removing of lithium and oxygen causes Li in composite material 2the net loss of O (" lithia "), and in such cases, the composite material in electrode form can be called as de-lithiumation.
Therefore, a kind of method characterizing the electrode formed by its composite material (such as formula III or formula IV material) can according to when charging to the battery comprising this type of electrode, and the degree of the de-lithiumation (if any) that electrode composite material experiences is expressed.Such as, this type of de-lithiumation can characterize under the following conditions: when existing as the negative electrode had in the electrochemical cell of lithium anodes, be charged to relative to Li/Li +for the electrode of 4.8V voltage is by de-for experience lithiumation, thus make to be expressed as (Li 2-wa 1- vb w+vo 3-e) the component of composite material be represented as (Li 2-w-ga 1-vb w+vo 3-e-g/2), wherein g is less than about 0.2.In various specific embodiment, battery can be charged to relative to Li/Li by lower charged state (multiplying power with such as 10mA/g composite material) +4.8V voltage, and/or electrode can experience de-lithiumation due to charging.
In the embodiment of other alternative, g is 0; Or g is 0 or higher, or be about 0.0001 or higher, or be about 0.001 or higher, or be about 0.01 or higher, or be about 0.05 or higher, and be also about 0.2 or lower, or be about 0.15 or lower, or be about 0.1 or lower.When g is 0, by (Li 2-wa 1-vb w+vo 3-e) component of composite material that represents is by de-lithiumation.
Characterizing the another kind of method of electrode that formed by its composite material (such as formula III or formula IV material) can according to after charging at battery, and the discharge capacity comprising the electrochemical cell of described electrode is expressed.Such as, the discharge capacity comprising the electrochemical cell of described electrode can characterize under the following conditions: when existing as the negative electrode had in the electrochemical cell of lithium anodes, described electrode:
A () is being enough to from being expressed as (Li ymn 2-zm zo 4-d) composite material component in remove Li +under the voltage of ion, be charged to y and be reduced to the degree being less than 0.2, and
B () is then discharged to relative to Li/Li with the multiplying power of the composite material of 10mA/g +the voltage of reference electrode 3.5V,
Participate in the electric discharge of electrochemical cell, make to be attributable to be expressed as (Li 2-wa 1-vb w+vo 3-e) nanocomposite constituents about 90mAh/g is less than to the contribution of discharge capacity.In various specific embodiment, battery can charge to charged state from lower charged state (multiplying power with such as 10mA/g composite material).
In the embodiment of other alternative, be attributable to be expressed as (Li 2-wa 1-vb w+vo 3-e) the contribution of the discharge capacity to electrochemical cell of electrode component be less than about 80mAh/g, or be less than about 60mAh/g, or be less than about 40mAh/g, or be less than about 20mAh/g, or be less than about 10mAh/g, or be less than about 5mAh/g, or be less than about 1mAh/g, or be less than about 0.5mAh/g, or be 0mAh/g.
Characterizing the another kind of method of electrode that formed by its composite material can according to after charging at battery, and the discharge capacity comprising the electrochemical cell of described electrode is expressed.Such as, when measuring with the multiplying power of 30mA/g or lower, the discharge capacity of this type of battery in 4.4 to 5.2 volt range is in the scope of about 60mAh/g to about 1000mAh/g.
In the embodiment of other alternative, when measuring with the multiplying power of 30mA/g or lower, the discharge capacity of the battery in 4.4 to 5.2 volt range is about 60mAh/g or higher, or be about 80mAh/g or higher, or be about 100mAh/g or higher, or be about 120mAh/g or higher, or be about 150mAh/g or higher, or be about 200mAh/g or higher, and be also about 1000mAh/g or lower.
As mentioned above, in any one any one electrode embodiment made in the composite material represented by formula III or IV described herein, or with in any one component of this type of composite material described in formula I or II, (Li 2-wa 1vb w+vo 3-e) component can have layer structure, and/or (Li ymn 2-zm zo 4-d) component can have spinel structure.
The electrochemical cell comprising the electrode prepared by its composite material is made up of following element, and described element comprises: (i) shell; (ii) two electrodes (anode and negative electrode); (iii) electrolyte composition of the ionic conduction path between anode and negative electrode is provided; Wherein two electrodes to be arranged in electrolyte composition and therefore ionic conduction contact each other; And (iv) porous barrier between anode and negative electrode.Shell can be any suitable container and remains on appropriate location with the assembly by electrochemical cell.
Porous barrier is for preventing the short circuit between anode and negative electrode.Porous barrier is made up of the single or multiple lift sheet material of microporous polymer usually.The aperture of described porous barrier is enough large to allow ion transmission, and enough little of to prevent contacting of anode and negative electrode, and described contact is directly contact or the contact from particle infiltration or dendron, and it can be formed on anode and negative electrode.
Store being used for and discharge the example being applicable to the active material of positive electrode preparing electrochemical cell as described herein of lithium ion, including but not limited to aluminium; Platinum; Palladium; Lithium metal; Lithiated carbon; Lithium alloy is lithium-aluminium alloy, lithium-lead alloy, lithium-silicon alloy, lithium-ashbury metal etc. such as; Material with carbon element such as graphite and MCMB (MCMB); Phosphorated material is black phosphorus, MNP such as 4with CoP 3; Metal oxide is SnO such as 2, SnO and TiO 2; And lithium titanate such as Li 4ti 5o 12and LiTi 2o 4.In one embodiment, the active material of positive electrode expected comprises lithium titanate or graphite.Suitable active material of positive electrode and anode can from company such as HitachiChemical (Tokyo, Japan), BTRNewEnergyMaterials (Tianjin, China), NEIInc. (Somerset, NJ) and FarasisEnergyInc. (Hayward, CA) is commercially available.
In electrochemical cell as disclosed herein, the negative electrode preferably prepared by its composite material.
Can such as by the electrode active material (such as about 70-96 % by weight) of effective dose, polymer base material (such as based on the copolymer such as polyvinylidene fluoride of PVF) and the conductive carbon in suitable solvent such as 1-METHYLPYRROLIDONE be mixed to form thickener to prepare for the electrode in electrochemical cell as disclosed herein.Described thickener is coated to metal forming, on preferred aluminium foil or Copper Foil, to be used as collector.Preferably use heat that thickener is dry, active material is bonded on collector, thus form electrode.
Electrochemical cell as disclosed herein also comprises electrolyte composition, is generally non-aqueous electrolyte composition, and it is for being applicable to the Chemical composition that providing ionic conductivity.Described electrolyte composition comprises at least one non-aqueous solvent and at least one electrolytic salt usually.Electrolytic salt is the mixture of ion salt or salt, and it to dissolve at least in part in the solvent of non-aqueous electrolyte composition and in the solvent of non-aqueous electrolyte composition, is dissociated into ion at least in part, to form conductivity electrolyte composition.Described conductivity electrolyte composition makes negative electrode and anode there is ionic conduction each other to contact, and make ion, lithium ion moves freely between the anode and cathode specifically, thus by described electrolyte composition conduct charges between the anode and cathode.Suitable electrolytic salt includes but not limited to:
Lithium hexafluoro phosphate,
LiPF 3(CF 2CF 3) 3、
Two (fluoroform sulphonyl) imine lithium,
Two (perfluoroethyl sulfonyl) imine lithium,
(fluoro sulphonyl) lithium
(nine fluorine fourth sulphonyl) imine lithium,
Two (fluoro sulphonyl) imine lithium,
LiBF4,
Lithium perchlorate,
Hexafluoroarsenate lithium,
Trifluoromethanesulfonic acid lithium,
Three (fluoroform sulphonyl) lithium methide,
Two (oxalic acid) lithium borate,
Difluoro (oxalic acid) lithium borate,
Li 2b 12f 12-xh x, wherein x equals 0 to 8, and
The mixture of lithium fluoride and anion receptor.
Any suitable electrolyte solvent or its mixture, can be used for forming dielectric composition, its example includes but not limited to ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate and dimethoxy-ethane.Other suitable electrolyte solvent comprise fluorated solvent such as fluorinated ether, fluoridize acyclic carboxylate, fluoridize acyclic carbonates and fluoridize cyclic carbonate.
Can for by with the compound of the representation of following formula with solvent version or the acyclic carboxylate of fluoridizing that is applicable to herein with the form of solvent mixture:
R 1---C(O)O---R 2
Wherein R 1be selected from CH 3, CH 2cH 3, CH 2cH 2cH 3, CH (CH 3) 2, CF 3, CF 2h, CFH 2, CF 2r 3, CFHR 3and CH 2r f; And
R 2independently selected from CH 3, CH 2cH 3, CH 2cH 2cH 3, CH (CH 3) 2and CH 2r f;
R 3for C 1to C 3alkyl group, it is optionally replaced by least one fluorine; And
R ffor the C replaced by least one fluorine 1to C 3alkyl group;
Precondition is R 1or R 2in at least one comprise at least one fluorine, and work as R 1for CF 2during H, R 2be not CH 3.
Be applicable to comprise those as the example of the specific fluorine-containing carboxylic acid ester of solvent herein, wherein
R 1for CH 3cH 2-and R 2for-CH 2cHF 2,
R 1for CH 3-and R 2for-CH 2cH 2cHF 2,
R 1for CH 3cH 2-and R 2for-CH 2cH 2cHF 2, or
R 1for CHF 2cH 2cH 2-and R 2for-CH 2cH 3.
In other embodiments, the cosolvent in mixture can be fluorine-containing carboxylic acid ester, and it is expressed from the next: R 4-COO-R 5, wherein R 4and R 5represent alkyl group independently, R 4and R 5middle carbon atom add up to 2 to 7, R 4and/or R 5in at least two hydrogen replaced by fluorine and R 4and R 5all do not comprise FCH 2or FCH group.It is believed that in carboxylate to there is single fluoroalkyl group (that is, FCH 2or FCH) cause toxicity.Therefore, suitable cosolvent includes but not limited to CH 3cH 2-COO-CF 2h (2,2-ethyl difluoro), CH 3cH 2-COO-CH 2cF 2h (2,2-difluoro ethyl propionate), F 2cHCH 2-COO-CH 3((3,3-difluoro methyl propionate), F 2cHCH 2-COO-CH 2cH 3(3,3-difluoro ethyl propionate), CH 3cH 2-COO-CH 2cF 2h (3,3-difluoroacetic acid propyl ester), CH 3cH 2-COO-CH 2cH 2cF 2h (3,3-difluoro propyl propionate) and F 2cHCH 2cH 2-COO-CH 2cH 3(4,4-difluoro ethyl butyrate).In certain embodiments, cosolvent is CH 3cH 2-COO-CF 2h (2,2-ethyl difluoro) or CH 3cH 2-COO-CH 2cF 2h
(2,2-difluoro ethyl propionate).In one embodiment, non-aqueous electrolyte composition solvent mixture with about 30: 70 weight ratio comprise ethylene carbonate and CH 3cH 2-COO-CF 2h (2,2-ethyl difluoro) or CH 3cH 2-COO-CH 2cF 2h (2,2-difluoro ethyl propionate), and comprise phosphate additive with about 1 % by weight.
Being applicable to herein can for by with the compound of the representation of following formula as the acyclic carbonates of fluoridizing of solvent:
R 4---O-C(O)O---R 5
Wherein R 4and R 5independently selected from CH 3, CH 2cH 3, CH 2cH 2cH 3, CH (CH 3) 2and CH 2r f, wherein R ffor the C replaced by least one fluorine 1to C 3alkyl group, and in addition, wherein R 4or R 5in at least one comprise at least one fluorine.
The suitable example of fluoridizing cyclic carbonate comprises fluoroethylene carbonate or by with the compound of the representation of following formula:
Wherein R is C 1to C 4fluoroalkyl group.
Other suitable electrolyte solvents are also described in U.S. Provisional Patent Application 61/530,545 and 61/654, and in 190, described document is incorporated to this paper as its part for all objects in full using way of reference.
Electrochemical cell disclosed herein can be used as various electronic equipment and goods, and (such as computer, electric tool, wind-force and solar energy transform the power supply of field, haulage vehicle (automobile, bus, train, steamer and aircraft) and telecommunication apparatus.
example
By a series of examples (example 1,2 and 11 ~ 15) as described below, can the operation of comprehend certain embodiments of the invention and effect.The embodiment of these Case-based Reasoning is only representational, and select those embodiments to carry out example the present invention, do not represent that the material be not described in these examples, component, reactant, conditioned disjunction specification are not suitable for the present invention, or do not represent within the theme that do not describe the in the illustration being described category not included in claims and equivalent thereof.By by the result obtained by described example with compare by some result obtained of filling a prescription the importance can understanding described example better, described formula Design becomes to be used as control experiment (example 3 ~ 8), and characterize owing to being made up of content difference, therefore can compare benchmark is provided to this.
The meaning of abbreviation used is as follows: " g " refers to gram, " mg " refers to milligram, " μ g " refers to microgram, " L " refers to liter, " mL " refers to milliliter, " mol " refers to mole, " mmol " refers to mM, " M " refers to molar concentration, " wt% " refers to percentage by weight, " Hz " refers to hertz, " mS " refers to milli Siemens, " mA " refers to milliampere, " mAh/g " refers to Milliampere Hour every gram, " V " refers to volt, " SOC " refers to charged state, " SEI " refers to the solid electrolyte interface formed on the surface of electrode material, " rpm " refers to revolutions per minute.
the preparation of negative electrode
First by active material of cathode (1.04g), the 0.13gDenkablack (acetylene black of preparation as described below, derive from DENKACorp., Japan), 1.08g polyvinylidene fluoride (PVDF) solution (12 % by weight 1-METHYLPYRROLIDONE (NMP) solution, KurehaAmericaInc., NewYork, NY, KFL#1120) and additional 2.3gNMP use planetary centrifugal mixer (THINKYARE-310, THINKYCorp., Japan) with 2000rpm mixing, then use shearing stirrer ( works, wilmington, NC) mix to form homogeneous slurry.By using doctor blade grid to be coated on aluminium foil by slurries, and then at 100 DEG C in convection oven dry 10 to 15 minutes.0.10mPa (15psi) lower roll calendering after, by the electrode of gained in vacuum drying oven at 90 DEG C under the Hg of-85kPa (-25 inches) further dry 6h.
shaping of composite cathode/Li anodic half-cell
By prepare as mentioned above negative electrode, dividing plate 2325 (Celgard, LLC.Charlotte, NC), lithium paper tinsel anode (0.75mm is thick) and several non-aqueous electrolyte compositions are clamped in 2032 stainless steel coin batteries tank (HohsenCorp., Japan) to form negative electrode/Li anodic half-cell.
example 1
0.03Li 2 mnO 3 0.97LiMn 1.5 ni 0.5 o 4 x-ray to spread out pattern
0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4the X-ray diffraction (XRD) of composite material is illustrated in Fig. 1.Cubic spinel is owing to LiMn 1.5ni 0.5o 4_, and lamellar phase is owing to Li 2mnO 3.Consistent for forming of forming of determining calculating with the stoichiometry based on initial substance by XRD.
example 2
0.03Li 2 mnO 3 0.97LiMn 1.5 ni 0.5 o 4 charge-discharge curves
Use comprises the standard electrolyte and 1MLiPF that volume ratio is carbonic acid ethyl ester (the EC)/ethylmethyl carbonate (EMC) of 30: 70 6(Novolyte, Cleveland, OH) prepares 0.03Li as mentioned above 2mnO 30.97LiMn 1.5ni 0.5o 4/ Li half-cell.Make this half-cell at 30mA/g and 25 DEG C, circulating between 3.5 and 4.95V.Typical charge-discharge curves is shown in Figure 2.Observe voltage platform at ~ 4.7V place, and discharge capacity is calculated as ~ 130mAh/g.
example 3 (comparative example)
liMn 1.5 ni 0.5 o 4 x-ray diffraction figure
LiMn 1.5ni 0.5o 4xRD be illustrated in Fig. 3.Cubic spinel is owing to LiMn 1.5ni 0.5o 4.Observe a small amount of Li 1-xni xo impurity.Consistent for forming of forming of determining calculating with the stoichiometry based on initial substance by XRD.
example 4 (comparative example)
liMn 1.5 ni 0.5 o 4 recharge-discharge fishing line
LiMn 1.5ni 0.5o 4/ Li half-cell uses and comprises the standard electrolyte and 1MLiPF that volume ratio is carbonic acid ethyl ester (the EC)/ethylmethyl carbonate (EMC) of 30: 70 6(Novolyte, Cleveland, OH) is prepared as mentioned above.Make this half-cell at 30mA/g and 25 DEG C, circulating between 3.5 and 4.95V.Typical charge-discharge curves is shown in Figure 4.Observe voltage platform at ~ 4.7V place, and discharge capacity is calculated as ~ 128mAh/g.Capacity is similar to 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4capacity because LiMn 1.5ni 0.5o 4there is few percent Li 1-xni xo impurity (see Fig. 3).
example 5 (comparative example)
0.1Li 2 mnO 3 0.9LiMn 1.5 ni 0.5 o 4 x-ray diffraction pattern
0.1Li 2mnO 30.9LiMn 1.5ni 0.5o 4the X-ray diffraction (XRD) of composite material is illustrated in Fig. 5.Cubic spinel is owing to LiMn i.5ni 0.5o 4, and lamellar phase is owing to Li 2mnO 3.Consistent for forming of forming of determining calculating with the stoichiometry based on initial substance by XRD.
example 6 (comparative example)
0.1Li 2 mnO 3 0.9LiMn 1.5 ni 0.5 o 4 charge-discharge curves
0.1Li 2mnO 30.9LiMn 1.5ni 0.5o 4/ Li half-cell uses and comprises the standard electrolyte and 1MLiPF that volume ratio is carbonic acid ethyl ester (the EC)/ethylmethyl carbonate (EMC) of 30: 70 6(Novolyte, Cleveland, OH) is prepared as mentioned above.Make this half-cell at 30mA/g and 25 DEG C, circulating between 3.5 and 4.95V.Typical charge-discharge curves is shown in Figure 6.Observe voltage platform at ~ 4.7V place, and discharge capacity is calculated as ~ 101mAh/g, this compares 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4the capacity of (~ 130mAh/g) is much lower.
This low capacity also show Li 2mnO 3the negligible electro-chemical activity of phase and poor electronic conductivity and Li ionic conductivity.Also point out only a small amount of Li 2mnO 3need the chemical property being optimized composite cathode by equilibrium chemistry stability and conductivity.
example 7 (comparative example)
0.5Li 2 mnO 3 0.5LiMn 1.5 ni 0.5 o 4 x-ray diffraction pattern
0.5Li 2mnO 30.5LiMn 1.5ni 0.5o 4the X-ray diffraction (XRD) of composite material is illustrated in Fig. 7.Cubic spinel is owing to LiMn 1.5ni 0.5o 4, and lamellar phase is owing to Li 2mnO 3.Consistent for forming of forming of determining calculating with the stoichiometry based on initial substance by XRD.
example 8 (comparative example)
0.5Li 2 mnO 3 0.5LiMn 1.5 ni 0.5 o 4 charge-discharge curves
0.5Li 2mnO 30.5LiMn 1.5ni 0.5o 4/ Li half-cell uses and comprises the standard electrolyte and 1MLiPF that volume ratio is carbonic acid ethyl ester (the EC)/ethylmethyl carbonate (EMC) of 30: 70 6(Novolyte, Cleveland, OH) is prepared as mentioned above.Make this half-cell at 30mA/g and 25 DEG C, circulating between 3.5 and 4.95V.Typical charge-discharge curves is shown in Figure 8.Observe voltage platform at ~ 4.7V place, and discharge capacity is calculated as ~ 70mAh/g, this present Li 2mnO 3electrochemistry nonactive, and capability value compares 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4the capability value of (~ 130mAh/g) is much lower.
example 9
xLi 2 mnO 3 (1-x) LiMn 1.5 ni 0.5 o 4 cycle performance compare
LiMn 1.5ni 0.5o 4, 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4, 0.1Li 2mnO 30.9LiMn 1.5ni 0.5o 4and 0.5Li 2mnO 30.5LiMn 1.5ni 0.5o 4cycle performance compare in fig .9.First known cycle performance increases then with 0.03Li 2mnO 3s increase and reduce, indicate a small amount of Li 2mnO 3liMn can be improved 1.5ni 0.5o 4cycle performance.
example 10
xLi 2 mnO 3 (1-x) LiMn 1.5 ni 0.5 o 4 multiplying power property compare
LiMn 1.5ni 0.5o 4, 0.03Li 2mnO 30.97LiMn 1.5ni 0.5o 4, 0.1Li 2mnO 30.9LiMn 1.5ni 0.5o 4and 0.5Li 2mnO 30.5LiMn 1.5ni 0.5o 4multiplying power property compare in Fig. 10.First multiplying power property increases then with Li 2mnO 3amount increase and reduce, indicate a small amount of Li 2mnO 3liMn can be improved 1.5ni 0.5o 4multiplying power property.
example 11
0.03Li 2 mnO 3 0.97LiMn 1.5 ni 0.45 fe 0.05 o 4 x-ray diffraction figure
0.03Li 2 mnO 3 0.97LiMn 1.5 ni 0.45 fe 0.05 o 4 the XRD of composite material is illustrated in Figure 11.Cubic spinel is owing to LiMn 1.5 ni 0.45 fe 0.05 o 4 , and lamellar phase is owing to Li 2mnO 3, wherein a small amount of Li and Mn is replaced by Ni.Consistent for forming of forming of determining calculating with the stoichiometry based on initial substance by XRD.
example 12
0 .03Li 2 mnO 3 0.97LiMn 1.5 ni 0.45 fe 0.05 o 4 eSEM
0.03Li 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the form of composite material is studied by ESEM and result is shown in Figure 12.Composite material crystallizes into octahedra shape.
example 13
0.03Li 2 mnO 3 0.97LiMn 1.5 ni 0.45 fe 0.05 o 4 charge-discharge curves
0.03Li 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4/ Li half-cell uses and comprises the standard electrolyte and 1MLiPF that volume ratio is carbonic acid ethyl ester (the EC)/ethylmethyl carbonate (EMC) of 30: 70 6(Novolyte, Cleveland, OH) is prepared as mentioned above.Make this half-cell at 30mA/g and 25 DEG C, circulating between 3.5 and 4.95V.Typical charge-discharge curves is shown in Figure 13.Observe voltage platform at ~ 4.7V place, and discharge capacity is calculated as ~ 132mAh/g.
example 14
0.03Li 2 mnO 3 0.97LiMn 1.5 ni 0.45 fe 0.05 o 4 cycle performance
0.03Li under room temperature 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the cycle performance of composite material is shown in Figure 14.Observe under 300 circulations ~ capacity of 96% retains, and shows extraordinary cycle performance.
example 15
0.03Li 2 mnO 3 0.97LiMn 1.5 ni 0.45 fe 0.05 o 4 multiplying power property
0.03Li is tested under various discharge current density 2mnO 30.97LiMn 1.5ni 0.45fe 0.05o 4the multiplying power property of composite material, and discharge curve is shown in Figure 15 a.Discharge capacity be normalized into the discharge capacity under 30mAh/g under different C multiplying powers and map (see Figure 15 b) relative to C multiplying power.Even if discharge at 10 DEG C, composite material also can transmit ~ 87% normalization capacity, and 0.03Li is compared in instruction 2mnO 30.97LiMn 1.5ni 0.5o 4(~ 80%) is rate capability better.
example 16
de-lithiumation calculates
The row instruction of following table 1
The composition of A cathode composite
B example number
C spinelle molar fraction
D negative electrode experiment first time charging capacity mAh/g
E spinel components formula weight g/mol
The formula weight g/mol of E layered component
The weight fraction of G spinel components
The contribution mAh/g to capacity that H is calculated by spinelle
I supposes by layered component the contribution mAh/g that the layered component of 50% de-lithiumation calculates
The capacity mAh/g of the calculating of the layered component of the de-lithiumation of J hypothesis 50%
table 1:
By observed by cathode material and the charging capacity calculated and comparative example and LiMn 1.5ni 0.5fe 0.05o 4compare (via coprecipitation preparation).If table 1 indicates for the de-expected charging capacity of lithiumation of part (row J) in first time charging of stratiform spinel composite material charging capacity of the viewed first time ratio layered component in row D example 2,6,8 and 13 low, and much lower in some cases.
Except the supplier that this paper other places are mentioned, the various metal and the metal-oxide compound that are applicable to the preparation of composite material (or its component) herein can be obtained by methods known in the art, and/or can from supplier as AlfaAesar (WardHill, Massachusetts), CityChemical (WestHaven, Connecticut), FisherScientific (Fairlawn, NewJersey), Sigma-Aldrich (St.Louis, or StanfordMaterials (AlisoViejo Missouri), California) commercially available.
In this manual, unless clearly indicated or indicated on the contrary in addition under use situation, wherein the embodiment of present subject matter be discussed or be described as to comprise, comprise, contain, have, by ... composition or be made up of some feature or key element, except clearly discuss or describe those except one or more feature or key element also can be present in embodiment.But an alternative embodiment of present subject matter can be discussed or be described as substantially to be made up of some feature or key element, embodiment feature or the key element that wherein greatly will change operating principle or the remarkable characteristic of embodiment are not then present in wherein.Another alternative embodiment of present subject matter can be discussed or be described as to be made up of some feature or key element, in described embodiment or its non-intrinsically safe modification, only there is the feature specifically discussed or describe or key element.
Each chemical formula shown in this article describes all different independent composite materials (or its component), described composite material (or its component) is combined into by following manner: (1) selects single value or value scope in variable groups, substituting group or numerical coefficient in specified scope, and every other variable groups, substituting group or numerical coefficient remain unchanged, (2) in specified scope, then each in other variable groups, substituting group or numerical coefficient is carried out to the selection of same-type, and other remain unchanged.Except except selecting single value or value scope in the specified scope of particular variable group, substituting group or a numerical coefficient of this paper formula, by carrying out selection to describe multiple composite material (or component) to single value or value scope in the specified scope of more than one variable groups, substituting group or the numerical coefficient in formula simultaneously.
The selection done in the specified scope of any variable groups, substituting group or the numerical coefficient in this paper formula is the subgroup that (i) to be included in the whole group membership of described scope only, or when (ii) being included in a more than member of whole group in described scope but being less than the subgroup of all members, selected member is not selected by selecting to be formed those other members of subgroup by neglecting in whole group.In the case, can also the definition of one or more variable group, substituting group or numerical coefficient be characterized by the described composite material (or its component) described in this class system of selection, it relates to variable whole group of specified scope, but points out that the member be left in the basket when forming subgroup is not in whole group.
In the shown in this article various formula that composite material (or its component) is described, the specified scope for each in the variable groups shown in formula, substituting group or numerical coefficient is all illustrated.By the composite material (or its component) described in this type of formula each density can according to can by as described in the maximum that wherein any one or multiple variable groups, substituting group or numerical coefficient specified in formula and minimum value any two combination any possible scope that formed express.Therefore, composite material (and component) herein comprises each in formula or all, wherein in variable groups, substituting group or numerical coefficient, the value of at least one is expressed together with any one or the maximum of other variable groups multiple, substituting group or numerical coefficient and this type of combination of minimum value by maximum as above and minimum value.
By in this paper specification of the performance characteristics of its sign, digital scope can be defined for the value being applicable to this class feature each at its various composite material.In this case, according to can by be applicable to as being attributed in the maximum of scope defined of value of selected characteristic and minimum value any two combination any possible range of being formed, particular composite is described.
As mentioned above, allly provide in this article or determine a certain number range part, described scope comprises its end points, and be positioned at all independent integer and the mark of described scope, and comprise by each being combined to form all various possible comparatively close limit of wherein these end points and internal integers and mark, to form the subgroup of larger numerical value group in the described scope of same degree, as clearly given these compared with each in close limit.When number range when is herein described to be greater than designated value, described scope remains limited, and is limited its upper limit by value practicable in the context of the invention as described herein.When number range when is herein described to be less than designated value, described scope is still limited its lower limit by nonzero value.
In the present note, unless explicitly pointed out separately or indicated on the contrary by the context used, the list of compound, monomer, oligomer, polymer and/or other chemical material, except any one the mixture of two or more in the corresponding derivative of any one and/or they in member, also comprises the derivative of member in list.

Claims (16)

1. one kind by with the composite material of the representation of following formula IV:
x(Li 2-wA 1-vB w+vO 3-e)·(1-x)(Li yMn 2-zM zO 4-d)IV
Wherein:
X is about 0.005 to about 0.08;
A comprises one or two member in the group be made up of Mn and Ti;
B comprise by Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V,
One or more members in the group of Zn, Zr and Y composition;
E is 0 to about 0.3;
V is 0 to about 0.5;
W is 0 to about 0.6;
M comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1; And
Wherein said Li ymn 2-zm zo 4-dcomponent has spinel structure and described Li 2-wb w+va 1- vo 3-ecomponent has layer structure.
2., for an electrode for electrochemical cell, it comprises the composite material by the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5;
W is 0 to about 0.6;
M comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0.9 to about 1; And
Z is about 0.3 to about 1; And
Wherein said Li ymn 2-zm zo 4-dcomponent has spinel structure and Li 2-wb w+va 1-vo 3-ecomponent has layer structure; And
Wherein when existing as the negative electrode had in the electrochemical cell of lithium anodes, be charged to relative to Li/Li +for the de-lithiumation of electrode experience of 4.8V voltage, thus make to be expressed as (Li 2-wa 1-vb w+vo 3-e) the component of composite material be represented as (Li 2-w-ga 1-vb w+vo 3-e-g/2), wherein g is less than about 0.2.
3., for an electrode for electrochemical cell, it comprises the composite material by the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises the one or more members in the group be made up of Mn and Ti;
B comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5;
W is 0 to about 0.6;
M comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0.9 to about 1; And
Z is about 0.3 to about 1; And
Wherein said Li ymn 2-zm zo 4-dcomponent has spinel structure and described Li 2-wb w+va 1- vo 3-ecomponent has layer structure; And
Wherein when existing as the negative electrode had in the electrochemical cell of lithium anodes, described electrode:
A () is being enough to from being expressed as (Li ymn 2-zm zo 4-d) composite material component in remove Li +under the voltage of ion, be charged to y and be reduced to the degree being less than 0.2, and
B () is then discharged to relative to Li/Li with the multiplying power of 10mA/g composite material +the voltage of reference electrode 3.5V,
Participate in the electric discharge of electrochemical cell, make to be attributable to be expressed as (Li 2-wa 1-vb w+vo 3-e) nanocomposite constituents about 90mAh/g is less than to the contribution of discharge capacity.
4. the composite material by the representation of following formula III:
(Li 2-wA 1-vB w+vO 3-e)·(Li yMn 2-zM zO 4-d)III
Wherein:
A comprises one or two member in the group be made up of Mn and Ti;
B comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr and Y;
E is 0 to about 0.3;
V is 0 to about 0.5;
W is 0 to about 0.6;
M comprises the one or more members in the group be made up of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr and Y;
D is 0 to about 0.5;
Y is 0 to about 1; And
Z is about 0.3 to about 1.
Wherein said (Li 2-wa 1vb w+vo 3-e) component has layer structure, and described (Li ymn 2- zm zo 4-d) component has spinel structure; And
Wherein said composite material have following characterize X-ray diffraction pattern // // ///
5. composition according to claim 1, wherein X is in the scope of about 0.005 to about 0.08.
6. composition according to claim 1, wherein said Li vmn 2-zm zo 4-dcomponent is cation disorder.
7. composition according to claim 1, wherein B is selected from the one or more members in the group be made up of Co, Cu, Fe, Ga and Ni; And/or
8. composition according to claim 1, wherein e is 0 or larger, and is also about 0.3 or less.
9. composition according to claim 1, wherein v is 0 or larger, and is also about 0.5 or less.
10. composition according to claim 1, wherein w is 0 or larger, and is also about 0.6 or less.
11. compositions according to claim 1, wherein M is selected from the one or more members in the group be made up of Co, Fe, Ga and Ni; And/or
12. compositions according to claim 1, wherein d is 0 or larger, and is also about 0.5 or less.
13. compositions according to claim 1, wherein y is 0 or larger, and is also about 1 or less.
14. compositions according to claim 1, wherein z is about 0.3 or larger, and is also about 1 or less.
15. 1 kinds of lithium-ions batteries, it comprises:
(a) shell;
(b) anode and negative electrode, described anode arranges in the housing with negative electrode and ionic conduction contacts each other, and wherein said negative electrode comprises composite material according to claim 1;
C () arranges in the housing and provides the non-aqueous electrolyte composition of the ionic conduction path between described anode and described negative electrode; With
(d) porous barrier between described anode and described negative electrode.
16. lithium-ions batteries according to claim 15, wherein said non-aqueous electrolyte composition comprises at least one electrolytic salt and at least one fluorinated ether, fluoridizes acyclic carboxylate, fluoridizes acyclic carbonates or fluoridize cyclic carbonate.
CN201480016049.4A 2013-03-15 2014-03-14 High voltage lithium ion battery Pending CN105051947A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US13/837,378 US9391322B2 (en) 2013-03-15 2013-03-15 Cathode material and battery
US13/837378 2013-03-15
PCT/US2014/027976 WO2014143834A1 (en) 2013-03-15 2014-03-14 High voltage lithium ion battery

Publications (1)

Publication Number Publication Date
CN105051947A true CN105051947A (en) 2015-11-11

Family

ID=51528454

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480016049.4A Pending CN105051947A (en) 2013-03-15 2014-03-14 High voltage lithium ion battery

Country Status (7)

Country Link
US (1) US9391322B2 (en)
EP (1) EP2973791A1 (en)
JP (1) JP6496921B2 (en)
KR (1) KR20150131031A (en)
CN (1) CN105051947A (en)
CA (1) CA2904136A1 (en)
WO (1) WO2014143834A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106910642A (en) * 2015-12-22 2017-06-30 比亚迪股份有限公司 A kind of ultracapacitor and preparation method thereof
CN114122328A (en) * 2020-08-31 2022-03-01 三星Sdi株式会社 Composition, positive electrode layer, all-solid-state secondary battery, and method for producing same

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9293236B2 (en) * 2013-07-15 2016-03-22 Semidonconductor Energy Laboratory Co., Ltd. Lithium—manganese composite oxide, secondary battery, and electric device
JP6195113B2 (en) * 2013-08-08 2017-09-13 トヨタ自動車株式会社 Positive electrode active material for lithium ion secondary battery
US10727465B2 (en) * 2013-11-15 2020-07-28 Semiconductor Energy Laboratory Co., Ltd. Nonaqueous secondary battery
CA2944454A1 (en) 2014-04-01 2015-10-08 The Research Foundation For The State University Of New York Electrode materials for group ii cation-based batteries
US9614229B2 (en) * 2014-09-30 2017-04-04 Maxpower, Inc. Functionalized short chain fluorinated polyether based electrolytes for safe lithium batteries and the cells having the same
JP6428192B2 (en) * 2014-11-20 2018-11-28 戸田工業株式会社 Positive electrode active material particle powder for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery
DE102015217745A1 (en) 2015-09-16 2017-03-16 Robert Bosch Gmbh Active material for a positive electrode of a battery cell, positive electrode and battery cell
CN105826534A (en) * 2016-04-28 2016-08-03 中国科学院金属研究所 Organic polymer sulfur/carbon nanotube composite material and application thereof to lithium sulfur battery
KR102538830B1 (en) 2016-07-05 2023-05-31 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Cathode active material, manufacturing method of cathode active material, and secondary battery
EP3485527A2 (en) * 2016-07-15 2019-05-22 Solvay SA Nonaqueous electrolyte compositions
DE202017007645U1 (en) 2016-10-12 2023-12-19 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material particles
KR20240046314A (en) 2017-05-12 2024-04-08 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Positive electrode active material particles
CN111900358A (en) 2017-05-19 2020-11-06 株式会社半导体能源研究所 Positive electrode active material and secondary battery
KR102223712B1 (en) 2017-06-26 2021-03-04 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Method for manufacturing positive electrode active material, and secondary battery
KR20200105482A (en) * 2018-01-12 2020-09-07 솔베이(소시에떼아노님) Non-aqueous electrolyte composition containing lithium bis(fluorosulfonyl)imide
US20240079580A1 (en) * 2021-09-05 2024-03-07 Worcester Polytechnic Institute Mixed cathode upcycling

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002124258A (en) * 2000-10-13 2002-04-26 Toda Kogyo Corp Lithium manganate particle powder and its manufacturing method
CN101080830A (en) * 2004-09-03 2007-11-28 芝加哥大学阿尔贡有限责任公司 Manganese oxide composite electrodes for lithium batteries
CN102812589A (en) * 2010-03-26 2012-12-05 Nec能源元器件株式会社 Non-aqueous electrolyte secondary battery
WO2013033595A1 (en) * 2011-09-02 2013-03-07 E. I. Du Pont De Nemours And Company Lithium ion battery

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3606289B2 (en) 1995-04-26 2005-01-05 日本電池株式会社 Cathode active material for lithium battery and method for producing the same
US6869547B2 (en) 1996-12-09 2005-03-22 Valence Technology, Inc. Stabilized electrochemical cell active material
JPH10172571A (en) 1996-12-16 1998-06-26 Aichi Steel Works Ltd Lithium secondary battery and manufacture of its positive electrode active material
EP0979815A1 (en) 1998-08-11 2000-02-16 Lonza A.G. Unsaturated oligophenolcyanates
US6964828B2 (en) 2001-04-27 2005-11-15 3M Innovative Properties Company Cathode compositions for lithium-ion batteries
WO2003015198A2 (en) 2001-08-07 2003-02-20 3M Innovative Properties Company Cathode compositions for lithium ion batteries
US7635536B2 (en) 2004-09-03 2009-12-22 Uchicago Argonne, Llc Manganese oxide composite electrodes for lithium batteries
US7935270B2 (en) * 2006-10-04 2011-05-03 Samsung Sdi Co., Ltd Cathode active material and lithium battery using the same
US10665892B2 (en) * 2007-01-10 2020-05-26 Eocell Limited Lithium batteries with nano-composite positive electrode material
JP2012209245A (en) * 2011-03-16 2012-10-25 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
JP5650077B2 (en) * 2011-08-23 2015-01-07 信越化学工業株式会社 Nonaqueous electrolyte secondary battery charging method and nonaqueous electrolyte secondary battery
JP5849542B2 (en) 2011-09-05 2016-01-27 株式会社Ihi Continuous heating furnace

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002124258A (en) * 2000-10-13 2002-04-26 Toda Kogyo Corp Lithium manganate particle powder and its manufacturing method
CN101080830A (en) * 2004-09-03 2007-11-28 芝加哥大学阿尔贡有限责任公司 Manganese oxide composite electrodes for lithium batteries
CN102812589A (en) * 2010-03-26 2012-12-05 Nec能源元器件株式会社 Non-aqueous electrolyte secondary battery
WO2013033595A1 (en) * 2011-09-02 2013-03-07 E. I. Du Pont De Nemours And Company Lithium ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106910642A (en) * 2015-12-22 2017-06-30 比亚迪股份有限公司 A kind of ultracapacitor and preparation method thereof
CN106910642B (en) * 2015-12-22 2019-06-07 比亚迪股份有限公司 A kind of supercapacitor and preparation method thereof
CN114122328A (en) * 2020-08-31 2022-03-01 三星Sdi株式会社 Composition, positive electrode layer, all-solid-state secondary battery, and method for producing same

Also Published As

Publication number Publication date
US20140272555A1 (en) 2014-09-18
WO2014143834A1 (en) 2014-09-18
EP2973791A1 (en) 2016-01-20
CA2904136A1 (en) 2014-09-18
JP2016518680A (en) 2016-06-23
JP6496921B2 (en) 2019-04-10
KR20150131031A (en) 2015-11-24
US9391322B2 (en) 2016-07-12

Similar Documents

Publication Publication Date Title
CN105051947A (en) High voltage lithium ion battery
US10347914B2 (en) Positive electrode active material for non-aqueous electrolyte secondary battery, process for producing the positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the positive electrode active material for non-aqueous electrolyte secondary battery
CN103636038B (en) Non-aqueous electrolyte battery positive active material, its manufacture method and use its non-aqueous electrolyte battery
CN105144457B (en) Nonaqueous electrolytic solution secondary battery
KR101945571B1 (en) Fluorinated electrolyte compositions
KR101938921B1 (en) Lithium ion battery
US10511020B2 (en) Nickel composite hydroxide particle and process for producing the same, positive electrode active material for non-aqueous electrolyte secondary battery and process for producing the same, and non-aqueous electrolyte secondary battery
KR101670327B1 (en) Composite cathode materials with controlled irreversible capacity loss for lithium ion batteries
CN104795550B (en) A kind of tunnel type oxide material and its production and use
CN103022455B (en) For the high magnification of lithium battery and the cathode material of high-energy
CN104681856B (en) Non-aqueous electrolyte secondary battery
CN109155412A (en) Non-aqueous electrolyte secondary battery positive active material and its manufacturing method, non-aqueous electrolyte secondary battery anode composite material paste and non-aqueous electrolyte secondary battery
US20120171542A1 (en) Secondary battery
CN105917515B (en) Non-aqueous electrolyte secondary battery and its group battery
CN105940528A (en) Nonaqueous-electrolyte secondary battery and method for manufacturing nonaqueous-electrolyte secondary battery
CN104169222A (en) Lithium composite oxide particle powder for non-aqueous electrolyte secondary battery and method for producing same, and non-aqueous electrolyte secondary battery
KR20080031616A (en) Cathode active material and lithium battery using the same
JP2008300180A (en) Nonaqueous electrolyte secondary battery
US9160000B2 (en) Active material for battery, and battery
JPWO2014017461A1 (en) Magnesium compound, method for producing the same, positive electrode active material, positive electrode, and magnesium ion secondary battery
CN106463780A (en) Non-aqueous electrolyte secondary battery, and battery pack obtained by connecting plurality of non-aqueous electrolyte secondary batteries
CN103931030A (en) Lithium ion secondary battery and method for manufacturing same
CN110061289A (en) Manufacturing method, nonaqueous electrolytic solution and the nonaqueous electrolytic solution secondary battery of nonaqueous electrolytic solution
US20110143192A1 (en) Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using the same
US20110136001A1 (en) Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20151111

RJ01 Rejection of invention patent application after publication